Process of adding hydrogen to fatty acids, fatty esters, and other unsaturated compounds.



C. ELLIS.

PROCESS OF ADDING HYDROGEN T0 FATTY ACIDS, FATTY ESTERS, AND OTHER UNSATURATED COMPOUNDS.

APPLICATION FILED APR. 5. 1912.

1,154,495. Patented Sept. 21, 1915.

In ventor:

' of Adding Hydrogen to Fatty Acids,

UNITED STATES gen'rizisrr OFFICE.-

cnmron Eli-1215,01 monrcnara, Y-NEW' mass f rnocsss or mains mnoenn r FATTY ACIDS, new ESTE unsa'rum'rnncomroonns.

as; AND OTHER To all whom it may concern:

Be it known that I, Gammon ELLIs, a citizen of the United States, and a lfcsident of Montclair, in the county of Essex and State of New Jersey, have invented certain new and useful Improvements in Profesises y Esters, and other Unsaturated Compounds, of which the foHowing is a specification.

This invention relates to a process of addinghydrogen to fatty acids, fatty esters and similar oils and. fats or other un-- saturated compounds, in the presence of I catalytic bodies capable of carrying hydrocatalyzers preferably being of an oil soluble,

gen to such material, and relates in particular to a process which involves the use of what may be termed potential catalyzers such for instance. as those which acquireac- 'tive properties only by'heating in a predetermined manner preferably in. the presence of the material to be hydrogenated so as .to form the catalyst in situ, such potential character and embracing suchbodies as nickel carbonyl.

In the present invention, it is particularly the object to provide a catalytic body which is capable of being decomposed by heat inthe presence of the oil to be treated and preferably likewise in the presence of hydrogen, or' a hydrogen containing gas, whereby metallic nickel in a finely divided form, or even in a nascent condition is secured.

Nickel carbonyl; is readily prepared by passing carbon monoxid over finely divided nickel at a temperature of 50 C.- orlso.

This compound, as is well known, isvolatile and mixes readily'withgases such as carbon monoxid, orhydrogen. It isdecomposed by heating to a temperature of 200 C., or even less, and when decomposed by heat under suitable conditions, the nickel is set ,free in a very finely divided metallic form. Nickel carbonyl .is readily soluble in many oily;

bodies and in carrying out one modification of the present invention, this nickel com-' pound to the extent of 1% to 2% or so,

based on the weight of the 'oil employed,-

may be mixed with oil andhydrogen gas contacted with themixture or solutlon, while at the same time the temperature ofthe oil.

is broughtto the point of decomposition ofthe nickel carbonyl; The nickelis :thus

"of about 200 "drogenat'ion of the if desired, finely divided solid material to downwardly flowing f tower, ;may;*be heated at one or more points Specification of Letters Patent. Pafentedsept, 21, 1915, Application ma April 5, 1912. Serial No. 688,814

separated and is at leastfor a time in a nascent condition, acting as a catalytic body and quickly causing hydrogen to enter the {oil molecule. For this purpose, ordinarily it 1s necessary to heat the oil to a temperature (3., to accomplish such decomposition.- Nickel carbonyl usually is not as easily decomposed when diluted as when heated in the pure state. Hence the temperature employed should be determined by the speed of decomposition of the; nickel carbonyl under the circumstances; that is to say both the character of the oiland 'the' degree of dilution" as well as pressure and [other conditions, should be considered.

Another modification of the present. in-' vention is. that ,of mixing the requisite amount of nickel carbonyl with hydrogen gas, or water gas, or other gas suitable for the purpose and then passing this'mixture into the oil tobe treated. .The oil is brought to the. decomposition} temperature of the nickel. carbonyl under these circumstances and thus the metallic j'nickel. catalyzer is liberated in intimate contact with-the hy drogengas, thereby-effecting a rapid hy- 0i1.-- The oil may contain,

serve as an attaching base for the deposited or separated'nickel. In case the finely di-' vided of colloidal nickel which'forms is not,

readily-removed by filafter hydrogenation,

be boiled with an aquetration,- the oil may terial.

bus acid; solution to remove such nickel ma- Another modification of thelpresent invention involves heating the oil to 180 C. or

so and atomizingsuch oil with a mixture of hydrogen gas and nickel'carbonyl. Or the a nickel carbonyl may be added'to the oil and the oil then atomized with hydrogen gas, the

temperature being regulated for the production of the active materialas above indicated.-- Af ter such atomization, the oil.

may. be passed through a heated tube org; over a bed of heated fragmental material.

Also thev oil may be mixed-with a .small amount of nickel carbonyl and caused to flow downwardly through a tower containing bafiles Iwhile hydrogen gasor other, gas

is allowed to. flow upwardly against the stream of 'oil; 'The so as to secure a temperature suflicient to decompose the nickel carbonyl and then, if desired, the temperature may be modified so that the mixture, on flowing through an-' other portion of the tower is subjected to a temperature better adapted for the hydrogenation process proper. The same operation may be conducted in an inclined tubeas described in Serial No. 656100, filed Oct. 23, 1911, which has matured into Letters Patent 1,026,156 of May 14, 1912, using means for diiferentially heating said tube.

This application is a continuation of the. Y

tinuous process and using water gas for hydrogenation, the residual gas, depleted of its hydrogen in a large-measure, may be used for preparing the nickel carbonyl compound. Nickel carbonyl may also be employed in a different way, in-that it may be mixed with asbestos or fullers earth, or other similar carrier and heated to form catalytic nickel without resorting to direct reduction of say nickel oxid by hydrogen. Such a catalytic body may then be used for treating oils in the presenceofhydrogen under suitable conditions of temperature and pressure. v

In the case of oleic acid or other bodies which may be converted into a vapor form, the nickel carbonyl and hydrogen may be mixed with the vapors of such bodies and passed through a heating zone, preferably being raised to a temperature of 180 or 200 degrees (1., or to whatever temperature under the particular conditions of operation is required for a satisfactory decomposition of the carbonyl compound into an active body. In this case also nascent nickel is liberated in the presence of tage.

Various oils may be treated in accordance with thepresent invention, the unsaturated fatty acids being treated, if desired in the form of their vapors under diminished .pressure. Fattyesters, such as corn and cotton seed oil, soy bean oil, fish oil, almond oil, peanut and mustard oils, castor oil, linseed and Chinese wood oils and the like are better treated in their liquid form, or sometimes in an atomized condition. As stated, it is desirable to regulate the temperature of decomposition of the nickel compound according to the particular condition of treatment, varying this according to the oil employed and the press ire of the hydrogen as gas. In some cases, as indicated, it is dehydrogen to good advanr sirable to decompose the potential catalyzer at a somewhat higher temperature than that needed for comple on of the hydrogenation. .I

In addition to nickel carbonyl, other volatile bodieshaving under certain conditions potentially catalytic properties, including the corresponding compounds of iron and i the like, and some of the compounds of metals with hydrocarbons,such for example as the methyl compoundsof the metals, as zinc methyl and the like may be employed.

The accompanying drawings show in diagrammatic manner apparatus with which the process of the present invention may be carried out.

Figure 1 is a vertical elevation of a tubular or tower-like apparatus provided with means for circulating oil and gas, and Fi 2 1s a vertical section of a closed receptac e or tank having means for circulating the gas.

nated by like characters.

In Fig. 1, i is a tube having the heating jacket 2. The tube may contain some frag- Like parts in the drawings are desigmental material as shown at 3. A'gas circuit shown at .4. and interposed in this conduit is the pump 5. An inlet for hydrogen or a hydrogen containing gas is shown at 6. This also maybe used for the introduction of nickel carbonyl and the. like, if

desired. ,An oil circuit is shown at 7, and

interposed in this conduit is the pump 8.

An oil inlet-is provided at 9 and if desired the catalyzer material 'may be introduced through this inlet. An oil outlet or draw of? is indicated at 10.

The operation is as follows: Oil in entered by 9 to fill the tube and oil conduit and is heated to the requisite temperature. Hydrogen is introduced at 6 and caused to circulate through the oil in the tube-1, entering the tube at the bottom thereof and being removed at the top. The oil circulatesin an opposite direction, entering the tube at the 'top and being removed at thebottom as it circulates in a cyclic manner through the treating apparatus. Nickel carbonyl is entered at 9 and mixes with the oil becoming decomposed by the temperature prevailing in the apparatus, whereupon hydrogenation of the oil takes place. i

In Fig. 2 the operation of the apparatus is as follows: Oil is charged into the tank 1 I to fill same nearly'full and the oil is heated, unless sufiiciently hot'when charged into the tank, until of the proper working or treating temperature. Nickel carbonyl in an amount of 12% or so in entered by the pipe 11. Hydrogen under pressure is in troduced by the inlet 12 and the gas is caused to circulate through the oil by means of the pump 5. The nickel carbonyl is decomposed after contacting with the oil for a time and the nickel material thus liberated in a finely divided condition enables the oil to be hydrogenated with ease.

Having described my invention, to the details of which I do not wish to be limited,

whatI claim is 1. The process of treating organic material containing normally liquid or solid unsaturated compounds which comprises thermally decomposing a potential catalyst in contact therewith in the presence of a hydrogen-containing gas, under suitable thermal conditions, whereby hydrogen is added to said unsaturated compounds.

2; The process of treating organic material containing normally liquid or solid unsaturated compounds which comprises thermally decomposing a potential catalyst of a lnetallo-organic naturewhereby an active metallic body is derived-in contact there with in the presence of hydrogen, under suitable thermal conditions, whereby hydregen is added to said unsaturated compounds.

, 3. The process of treating organic material containing normally liquid or solid unsaturated compounds which comprises thermally decomposing a potentialcatalyst of a metallo-organic naturew'hereby an active metallic body in a state of extreme subdivision is derivedin contact therewith in the presence of ahydrogen-containing gas, under suitable thermal conditions, whereby hydrogen is added to said unsaturated compounds.

86 l l. The process of treating organic material containing normally liquid or solid unsaturated compounds which comprises thermally decomposing nickel carbonylwhereby nickel in a state of extreme sub-division is derivedin contact therewith in the presence of a hydrogen-containing gas, under suitable thermal conditions, whereby hydrogen is added to said unsaturated compounds.

Theprocess of treating oily and fatty material containing unsaturated compounds which comprises thermally decomposing nickel carbonyl-whereby active nickel ma terial in a state of extreme sub-division is derivedin contact therewith in the presence of hydrogen, whereby hydrogen is added to said unsaturated compounds.

6. The process oftreating oily and fatty material containing unsaturated compounds which comprises thermally decomposing nickel carbonyl whereby an active nickel body in a state of extreme sub-division is derivedin contact therewith in the presence of a hydrogen-containing gas, undersuitable thermal conditions, whereby hydrogen is added to said unsaturated compounds.

.7. The process of treating oily and fatty material containing unsaturated compounds -which comprises thermally decomposing nickel carbonyl-whereby an active nickel body is derivedand in contacting said nickel body while in a nascent condition,

with said material in the presence of a hydrogen-containing gas, under suitable thermal conditions, whereby hydrogen is added to said unsaturated compounds.

8. The process of treating oily and fatty material containing unsaturated compounds which comprises thermally decomposing nickel carbonylwhcreby an active nickel body is derivedin contact therewith in the presence of hydrogen under pressure and .under suitable thermal conditions, whereby hydrogen is added to said unsaturated compounds.

9. A process of catalytic hydrogenation which consists in heating the substance to be hydrogenated together with a hydrogenatg agent and as the sole catalytic agenta metal carbonyl.

10. A process of catalytic hydrogenation which consists in heating the substance to be hydrogenated together with a hydrogenating agent and as the 'sole catalytic agent nickel carbonyl.

11. A process of catalytic hydrogenation of fatty bodies which consists 1n bringing simultaneously into contact the hydrogenating agent, nickel carbonyl as the sole catalytic agent, and the 'fatty body at a temperanating agent, in the presence of nickel carbonyl at the moment of its decomposition by heat, as the sole catalytic agent.

14. A process of catalytic hydrogenation which consists in heating the substance to be' hydrogenated together with a hydrogenatingagent and as the sole catalytic agent, in

the presence of a gaseous or vaporous me tallic compound which is decomposed with liberation of metal at the temperature used.

15. The process of treating unsaturated fatty material which comprises mixing therewith nickel carbonyl and hydrogen, in pro- I portions suitable for effecting hydrogena tion of the unsaturated fatty material, de-

composing the nickel carbonyl,- whereby vnickel in nascent condition is liberated within the unsaturated material while the same is in contact with hydrogenand subjecting the material under treatment to the joint action of the nickel and the hydrogen.

16. The process of treating unsaturated fatty material which comprises mixing therewith nickel carbonyl and a hydrogen containing gas and subjecting the mixture to heat and pressure in excess of atmospheric pressure for a considerable period of time.

17. The process of treating unsaturated 5 fatty material which comprises mixing therewith nicke1 carb0ny1--and a. hydrogen ;bonyl for a considerable period of time and simultaneously subjecting the mixture to pressure" in excess of atmospheric pressure and agitation.

7 w heat, pressure in excess of atmospheric prescontaining gas and. subjecting the mixture to Signed at Montclair in the county of Es- ,sex and State of New Jersey, this 3rd day of April, A; D. 191 2.

- CARLETON ELLIS.

sure, and agitation fora considerable period J0 oftime. p I

18. The process of treating unsaturated fatty material which consists in bringin a hydrogen containing gas laden with nic e1 carbonyl into contact therewith, maintain Witnesses:

BIRDELLA M; ELLIS, OLIVE J. HAWTHORN. 

